CN103910823A - Preparation method and application of polar group-modified pendent double bond post-crosslinked polydivinylbenzene resin - Google Patents
Preparation method and application of polar group-modified pendent double bond post-crosslinked polydivinylbenzene resin Download PDFInfo
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Abstract
The invention discloses a preparation method and an application of polar group-modified pendent double bond post-crosslinked polydivinylbenzene resin. The preparation method comprises: firstly performing a polymerization reaction of divinylbenzene monomers, polar monomers, and a pore forming agent to obtain a polar group-modified pendent double bond post-crosslinked polydivinylbenzene resin precursor; performing further crosslinking through a Friedel-Crafts reaction to obtain the polar group-modified pendent double bond post-crosslinked polydivinylbenzene resin. The preparation method is simple, and low in cost, and the prepared post-crosslinked resin has a high specific surface area and a special pore structure; the post-crosslinked resin can be used for adsorbing and removing organic matter in waste water, has the effect of selective adsorption, and especially has obvious selective adsorption effect on Congo red and/or rhodamine B.
Description
Technical field
The present invention relates to after a kind of polar group is modified suspended double bond be cross-linked the preparation method and the application that gather divinylbenzene resin, belong to macromolecule modified field.
Background technology
After suspended double bond, first crosslinking is put forward by Ando.In recent years, the Yan Jun seminar of China utilizes AMBERLITE XAD-4 to carry out crosslinking reaction after suspended double bond, but because the precursor of rear cross-linked resin is all nonpolar, the rear cross-linked resin of preparation has extremely strong hydrophobicity, be unfavorable in industrial use, and limited to thering is the adsorptive power of organic compound of certain polarity.For this reason, to cross-linked resin after suspended double bond carry out Modified with Polar Monomer to improve resin particularly important to the adsorptive power of polar adsorption matter.
At present, that in domestic and foreign literature, cross-linked resin after the suspended double bond of Modified with Polar Monomer is reported is considerably less, Zeng little Wei etc. have synthesized the rear cross-linked resin that methyl methacrylate, NVP isopolarity monomer are modified, but these rear cross-linked resin specific surface areas of carrying out after monomer polarity modification decline obviously, therefore increase not obvious to the adsorptive power of polar organic matter (as: phenol), what have even has a reduction, and along with the consumption of polar monomer changes adsorptive power significant difference.
Summary of the invention
Be all nonpolar body mostly for rear cross-linked adsorbing resin of the prior art, exist hydrophobicity strong, and a little less than the adsorptive power of polar organic compound, the defect that application is limited to, the object of the invention is to be to provide a kind of simple, cost lowly to prepare high-specific surface area, there is special pore structure, and after modifying suspended double bond to the polar group of polar organic compound selective adsorption, be cross-linked the method for gathering divinylbenzene resin, the method meets suitability for industrialized production.
Another object of the present invention is to be cross-linked the application that gathers divinylbenzene resin after being to provide described polar group to modify suspended double bond, described polar group is cross-linked the polar adsorption matter in the poly-divinylbenzene resin energy selective adsorption aqueous solution after modifying suspended double bond, particularly Congo red and/or rhodamine B, and easily wash-out, resin can be reused.
The invention provides after a kind of polar group is modified suspended double bond and be cross-linked the preparation method who gathers divinylbenzene resin, this preparation method be first the mixing oil of divinylbenzene monomer, polar monomer, toluene, normal heptane and initiator was communicated dispersion agent dispersed with stirring in 40～50 ℃ of water after, under agitation condition, be first warmed up to 68～75 ℃ of polyreactions, be warmed up to again 83～87 ℃ of polyreactions, be more further warmed up to 90～95 ℃ and boil ball; After polyreaction completes, reaction product is washed, solvent extraction, obtains after polar group is modified suspended double bond being cross-linked poly-divinylbenzene resin precursor; Gained presoma, by after solvent-swollen, adds Lewis acid to carry out Friedel-Crafts reaction as catalyzer at 80～85 ℃; After Friedel-Crafts reaction completes, by products therefrom washing, solvent extraction, obtain after polar group is modified suspended double bond and be cross-linked poly-divinylbenzene resin; Described polar monomer is one or more in triallyl isocyanurate, glycidyl methacrylate, methyl acrylate, vinyl acetate; Described polar monomer is 5～20% of divinylbenzene monomer and polar monomer total mass.
Described polar monomer is preferably 5～10% of divinylbenzene monomer and polar monomer total mass; Most preferably be 5～7%.
Preferred Lewis acid is iron trichloride, aluminum chloride, tin tetrachloride etc.
Described Lewis acid add-on is 0.2～0.3 times of presoma quality.
In preferred preparation method, the total mass of first benzene and heptane is 150～250% of divinylbenzene monomer and polar monomer total mass, and the mass ratio of first benzene and heptane is 3～4:1.
Described initiator is benzoyl peroxide, azo isobutyronitrile etc.
Described initiator amount is 0.5～1.0% of divinylbenzene monomer and polar monomer total mass.
Described dispersion agent is polyvinyl alcohol.
The mass percent concentration of described dispersion agent in the aqueous solution is 0.8～1.2%.
After described polar group modification suspended double bond, crosslinked poly-divinylbenzene resin pore size distribution is 1～45nm, and mean pore size is 6～13nm, and specific surface area is 700～1200m
2/ g, pore volume is 1.6～2.5cm
3/ g.
The solvent of described swelling employing is ethylene dichloride.
After the polar group modification suspended double bond that the present invention also provides described preparation method to make, be cross-linked the application of poly-divinylbenzene resin, this application is that after polar group is modified to suspended double bond, crosslinked poly-divinylbenzene resin is applied to the organic adsorbate of polarity in the adsorbing and removing aqueous solution.
After preferred polar group modification suspended double bond, crosslinked poly-divinylbenzene resin pore size distribution is 1～45nm, and mean pore size is 6～13nm, and specific surface area is 700～1200m
2/ g, pore volume is 1.6～2.5cm
3/ g.
The preferred organic adsorbate of polarity is Congo red and/or rhodamine B.
Polar group of the present invention is cross-linked the preparation method who gathers divinylbenzene resin after modifying suspended double bond, comprises the following steps:
Step 1: by the oil mixture of divinylbenzene (DVB) monomer, polar monomer, toluene, normal heptane and initiator composition, under agitation condition, joining temperature is 40～50 ℃, and in the polyvinyl alcohol water solution that mass percent is 0.8～1.2%, adjusting stirring velocity is 100～140r/min, is slowly warming up to 68～75 ℃, polyreaction 2～3h, be warming up to again 83～87 ℃, keep 3～5h; Further be warming up to 90～95 ℃, boil ball 2～3h; After having reacted, incline and reaction mother liquor, adopt hot water and cold water repetitive scrubbing spherical resin, then use Petroleum ether extraction pore-creating agent toluene and normal heptane, dry polar group is modified crosslinked poly-divinylbenzene resin precursor after suspended double bond; Described polar monomer is 5～20% of divinylbenzene monomer and polar monomer total mass; The total mass of first benzene and heptane is 150～250% of divinylbenzene monomer and polar monomer total mass, and wherein, the mass ratio of first benzene and heptane is 3～4:1; Described initiator amount is 0.5～1.0% of divinylbenzene monomer and polar monomer total mass;
Step 2: be cross-linked poly-divinylbenzene resin precursor after modifying suspended double bond with the swelling polar group of ethylene dichloride, under 35～45 ℃ of temperature condition, add lewis acid catalyst, stirring and dissolving 0.5～1h; Be warming up to again 80～85 ℃ of reaction 10～15h; After having reacted, replace washing resin 3～5 times with massfraction 1% hydrochloric acid soln and dehydrated alcohol, with dehydrated alcohol extracting 10～15h, dry polar group is modified crosslinked poly-divinylbenzene resin after suspended double bond.
Beneficial effect of the present invention: the present invention introduces first after appropriate polar monomer first makes polar group modification suspended double bond and is cross-linked poly-divinylbenzene resin precursor in poly-divinylbenzene, again by suspended double bond remaining in precursor resin is carried out to rear crosslinking reaction, obtaining one has compared with bigger serface, and have again certain polarity, the polar group that can carry out selective adsorption to the organic adsorbate of polarity is modified crosslinked poly-divinylbenzene resin after suspended double bond.The present invention is first under appropriate pore-creating agent effect, make wide-aperture resin precursor, again by rear crosslinking reaction, after polar group is modified to suspended double bond, crosslinked wide aperture of gathering divinylbenzene resin precursor is almost all filled, and produce a large amount of micropores, mean pore size is 6～13nm, and specific surface area is increased to 700～1200m
2the specific surface area of/g(presoma is 400～600m
2/ g), pore volume is 1.6～2.5cm
3/ g; Simultaneously, the introducing of appropriate polar monomer, on the one hand pore size distribution is regulated, increase on the other hand polymer polarity, energy selective adsorption polarity organic matter, particularly when the introduction volume of polar monomer account for monomer total mass 5～10% time (5～7% optimum), obvious especially to selective adsorption effect Congo red, rhodamine B; And easy wash-out after crosslinked poly-divinylbenzene resin absorption after this polar group modification suspended double bond, resin is reusable, has broad prospect of application in improvement and the resource utilization field of waste water from dyestuff.In addition, preparation method of the present invention is simple, cost is low, meets suitability for industrialized production.
Accompanying drawing explanation
[Fig. 1] is that after nonpolar rear crosslinked front and back resin and polar group of the present invention are modified suspended double bond, crosslinked infrared spectrogram of gathering divinylbenzene resin: PDVB gathers divinylbenzene resin; PDVB_pc is cross-linked resin after poly-divinylbenzene; PDVB/GMA_pc is that the methacrylic acid acid glycidyl ester polar group prepared of embodiment 1 is modified crosslinked poly-divinylbenzene resin after suspended double bond; PDVB/TAIC_pc is that the triallyl isocyanurate polar group prepared of embodiment 2 is modified crosslinked poly-divinylbenzene resin after suspended double bond.
[Fig. 2] is the infrared spectrogram of crosslinked poly-divinylbenzene resin after nonpolar rear cross-linked resin and methacrylic acid acid glycidyl ester polar group of the present invention modification suspended double bond: PDVB_pc is cross-linked resin after poly-divinylbenzene; PDVB/GMA_pc-5% is that massfraction 5% methacrylic acid acid glycidyl ester polar group prepared by embodiment 1 is modified crosslinked poly-divinylbenzene resin after suspended double bond; PDVB/GMA_pc-10% is that massfraction 10% methacrylic acid acid glycidyl ester polar group prepared by embodiment 5 is modified crosslinked poly-divinylbenzene resin after suspended double bond.
[Fig. 3] is that after nonpolar rear crosslinked front and back resin and polar group of the present invention are modified suspended double bond, crosslinked graph of pore diameter distribution (acquisition of BJH method) of gathering divinylbenzene resin: PDVB gathers divinylbenzene resin; PDVB_pc is cross-linked resin after poly-divinylbenzene; PDVB/GMA_pc is that the methacrylic acid acid glycidyl ester polar group prepared of embodiment 1 is modified crosslinked poly-divinylbenzene resin after suspended double bond; PDVB/TAIC_pc is that the triallyl isocyanurate polar group prepared of embodiment 2 is modified crosslinked poly-divinylbenzene resin after suspended double bond.
[Fig. 4] be nonpolar rear cross-linked resin and polar group of the present invention modify after suspended double bond crosslinked poly-divinylbenzene resin to adsorption isothermal line Congo red in the aqueous solution: PDVB_pc for poly-divinylbenzene after cross-linked resin; PDVB/GMA_pc is that the glycidyl methacrylate polar group prepared of embodiment 1 is modified crosslinked poly-divinylbenzene resin after suspended double bond; PDVB/TAIC_pc is that the triallyl isocyanurate polar group prepared of embodiment 2 is modified crosslinked poly-divinylbenzene resin after suspended double bond.
[Fig. 5] is that after nonpolar rear cross-linked resin and polar group of the present invention modification suspended double bond, the adsorption isothermal line of crosslinked poly-divinylbenzene resin to rhodamine B in the aqueous solution: PDVB_pc is cross-linked resin after poly-divinylbenzene; PDVB/GMA_pc is that the methacrylic acid acid glycidyl ester polar group prepared of embodiment 1 is modified crosslinked poly-divinylbenzene resin after suspended double bond; PDVB/TAIC_pc is that the triallyl isocyanurate polar group prepared of embodiment 2 is modified crosslinked poly-divinylbenzene resin after suspended double bond.
[Fig. 6] modifies crosslinked poly-divinylbenzene resin after suspended double bond for methacrylic acid acid glycidyl ester polar group of the present invention is that methacrylic acid acid glycidyl ester polar group prepared by embodiment 1 is modified crosslinked poly-divinylbenzene resin after suspended double bond to adsorption isothermal line Congo red in the aqueous solution: PDVB/GMA; PDVB/GMA_pc is that the methacrylic acid acid glycidyl ester polar group prepared of embodiment 1 is modified crosslinked poly-divinylbenzene resin after suspended double bond.
[Fig. 7] for methacrylic acid acid glycidyl ester polar group of the present invention modify after suspended double bond crosslinked poly-divinylbenzene resin to adsorption isothermal line Congo red in the aqueous solution: PDVB_pc for poly-divinylbenzene after cross-linked resin; PDVB/GMA_pc-5% is that massfraction 5% methacrylic acid acid glycidyl ester polar group prepared by embodiment 1 is modified crosslinked poly-divinylbenzene resin after suspended double bond; PDVB/GMA_pc-10% is that massfraction 10% methacrylic acid acid glycidyl ester polar group prepared by embodiment 5 is modified crosslinked poly-divinylbenzene resin after suspended double bond; PDVB/GMA_pc-20% is that massfraction 20% methacrylic acid acid glycidyl ester polar group prepared by embodiment 6 is modified crosslinked poly-divinylbenzene resin after suspended double bond.
The triallyl isocyanurate polar group that [Fig. 8] prepared for the embodiment of the present invention 2 is cross-linked the adsorptive power curve of poly-divinylbenzene resin (PDVB/TAIC_pc) to the circulation of five of rhodamine B in the aqueous solution continuous absorption/desorption after modifying suspended double bond.
Embodiment
Following examples are intended to further illustrate content of the present invention, rather than limit the scope of the invention.
Embodiment 1
The preparation of glycidyl methacrylate and divinylbenzene copolymer (PDVB/GMA): the aqueous solution that adds 200mL1%PVA in the 500mL there-necked flask that reflux condensing tube, thermometer and mechanical stirrer are housed, be warming up to 45 ℃, under agitation add the mixing oil phase of 19g DVB, 1g polar monomer GMA, toluene (quality be monomer total mass 160%), normal heptane (quality be monomer total mass 40%) and benzoyl peroxide (quality be monomer total mass 1.0%), adjusting stirring velocity is 100r/min, controls the size of oil droplet.Slowly be warming up to 75 ℃ of polymerization 2h; Be warming up to again 85 ℃ of polyase 13 h; Continue to be warming up to 95 ℃ and boil ball 3h.Pour out product, use respectively hot water, cold water washing, and remove pore-creating agent with Petroleum ether extraction 24h, be drying to obtain precursor resin PDVB/GMA.Record the mean pore size 8.1nm of precursor resin, pore size distribution 2～60nm, Brunauer-Emmett-Teller(BET) specific surface area 584m
2/ g, pore volume 1.51cm
3/ g.
Glycidyl methacrylate polar group is modified the preparation of crosslinked poly-divinylbenzene resin (PDVB/GMA_pc) after suspended double bond: take a certain amount of precursor resin, add enoughly 1,2-ethylene dichloride solvent-swollen spends the night.At 35 ℃, add 0.3 times of FERRIC CHLORIDE ANHYDROUS to make catalyzer, stirring and dissolving 1h.Be warming up to 80 ℃ of polymerization 12h.Replace washing resin 3 times with 1% hydrochloric acid soln and dehydrated alcohol respectively, with dehydrated alcohol extracting 12h, dry glycidyl methacrylate polar group is modified crosslinked poly-divinylbenzene resin after suspended double bond.Record the mean pore size 6.7nm of PDVB/GMA_pc resin, pore size distribution 1-45nm, BET specific surface area 791m
2/ g, pore volume 1.74cm
3/ g.
Synthetic resins is to Congo red adsorption isothermal line: get one group of tool plug Erlenmeyer flask, add respectively therein the Congo red aqueous solution of 0.1000g dried resin and 50.00mL different concns, they are placed in to rotary water bath vibrator, and constant temperature oscillation 24h under 298K, makes absorption reach balance.Measure the absorbancy of the rear raffinate of absorption with ultraviolet-visual spectrometer at Congo red maximum absorption wavelength 496nm place, and be converted into the equilibrium concentration C of adsorbate according to typical curve
e, and calculated equilibrium adsorptive capacity q (mg/g)
e(mg/g).With equilibrium concentration C
efor X-coordinate, adsorptive capacity q
efor ordinate zou, make this resin under 298K to the aqueous solution in Congo red adsorption isothermal line.
Embodiment 2
The preparation of triallyl isocyanurate and divinylbenzene copolymer (PDVB/TAIC): the aqueous solution that adds 200mL0.8%PVA in the 500mL there-necked flask that reflux condensing tube, thermometer and mechanical stirrer are housed, be warming up to 45 ℃, under agitation add the mixing oil phase of 19g DVB, 1g polar monomer TAIC, toluene (quality be monomer total mass 200%), normal heptane (quality be monomer total mass 50%) and azo isobutyronitrile (quality be monomer total mass 0.5%), regulate stirring velocity 120r/min, control the size of oil droplet.Slowly be warming up to 70 ℃ of polyase 13 h; Be warming up to again 87 ℃ of polymerization 4h; Continue to be warming up to 90 ℃ and boil ball 3h.Pour out product, use respectively hot water, cold water washing, and remove pore-creating agent with Petroleum ether extraction 24h, be drying to obtain precursor resin PDVB/TAIC.Record the mean pore size 4.9nm of precursor resin, pore size distribution 1.7-40nm, Brunauer-Emmett-Teller(BET) specific surface area 513m
2/ g, pore volume 0.75cm
3/ g.
Triallyl isocyanurate polar group is modified the preparation of crosslinked poly-divinylbenzene resin (PDVB/TAIC_pc) after suspended double bond: take a certain amount of precursor resin, add enoughly 1,2-ethylene dichloride solvent-swollen spends the night.At 45 ℃, add 0.2 times of Aluminum chloride anhydrous to make catalyzer, stirring and dissolving 0.5h.Be warming up to 85 ℃ of polymerization 10h.Replace washing resin 4 times with 1% hydrochloric acid soln and dehydrated alcohol respectively, with dehydrated alcohol extracting 15h, dry triallyl isocyanurate polar group is modified crosslinked poly-divinylbenzene resin after suspended double bond.Record the mean pore size 7.5nm of PDVB/TAIC_pc resin, pore size distribution 1-30nm, BET specific surface area 1019m
2/ g, pore volume 2.28cm
3/ g.
The adsorption isothermal line of synthetic resins to rhodamine B: get one group of tool plug Erlenmeyer flask, add respectively therein the rhodamine B aqueous solution of 0.1000g dried resin and 50.00mL different concns, they are placed in to rotary water bath vibrator, and constant temperature oscillation 24h under 298K, makes absorption reach balance.Measure the absorbancy of the rear raffinate of absorption with ultraviolet-visual spectrometer at the maximum absorption wavelength 554nm place of rhodamine B, and be converted into the equilibrium concentration C of adsorbate according to typical curve
e, and calculated equilibrium adsorptive capacity q (mg/g)
e(mg/g).With equilibrium concentration C
efor X-coordinate, adsorptive capacity q
efor ordinate zou, make this resin under 298K to the aqueous solution in the adsorption isothermal line of rhodamine B.
The regeneration of PDVB/TAIC_pc resin: after the triallyl isocyanurate polar group modification suspended double bond after absorption rhodamine B, crosslinked poly-divinylbenzene resin leaches to dry and is placed in 100mL tool plug Erlenmeyer flask, the spirituous solution vibration 6h that adds 50mL60%, the resin after regeneration continues on for the removal of rhodamine B after drying.
Embodiment 3
The preparation of methyl acrylate and divinylbenzene copolymer (PDVB/MA): the aqueous solution that adds 200mL1.2%PVA in the 500mL there-necked flask that reflux condensing tube, thermometer and mechanical stirrer are housed, be warming up to 45 ℃, under agitation add the mixing oil phase of 19g DVB, 1g polar monomer MA, toluene (quality be monomer total mass 150%), normal heptane (quality be monomer total mass 50%) and benzoyl peroxide (quality be monomer total mass 0.5%), regulate stirring velocity 125r/min, control the size of oil droplet.Slowly be warming up to 68 ℃ of polyase 13 h; Be warming up to again 83 ℃ of polymerization 5h; Continue to be warming up to 95 ℃ and boil ball 3h.Pour out product, use respectively hot water, cold water washing, and remove pore-creating agent with Petroleum ether extraction 24h, be drying to obtain precursor resin PDVB/MA.Record the mean pore size 8.5nm of precursor resin, pore size distribution 2-65nm, Brunauer-Emmett-Teller(BET) specific surface area 532m
2/ g, pore volume 1.36cm
3/ g.
Methyl acrylate polar group is modified the preparation of crosslinked poly-divinylbenzene resin (PDVB/MA_pc) after suspended double bond: take a certain amount of precursor resin, add enoughly 1,2-ethylene dichloride solvent-swollen spends the night.At 40 ℃, add 0.2 times of FERRIC CHLORIDE ANHYDROUS to make catalyzer, stirring and dissolving 0.5h.Be warming up to 80 ℃ of polymerization 12h.Replace washing resin 5 times with 1% hydrochloric acid soln and dehydrated alcohol respectively, with dehydrated alcohol extracting 15h, dry methyl acrylate polar group is modified crosslinked poly-divinylbenzene resin after suspended double bond.Record the mean pore size 6.8nm of PDVB/MA_pc resin, pore size distribution 1-35nm, BET specific surface area 738m
2/ g, pore volume 1.72cm
3/ g.
Synthetic resins is to Congo red adsorption isothermal line: get one group of tool plug Erlenmeyer flask, add respectively therein the Congo red aqueous solution of about 0.1000g dried resin and 50.00mL different concns, they are placed in to rotary water bath vibrator, and constant temperature oscillation 24h under 303K, makes absorption reach balance.Measure the absorbancy of the rear raffinate of absorption with ultraviolet-visual spectrometer at Congo red maximum absorption wavelength 496nm place, and be converted into the equilibrium concentration C of adsorbate according to typical curve
e, and calculated equilibrium adsorptive capacity q (mg/g)
e(mg/g).With equilibrium concentration C
efor X-coordinate, adsorptive capacity q
efor ordinate zou, make this resin under 303K to the aqueous solution in Congo red adsorption isothermal line.
Embodiment 4
The preparation of vinyl acetate and divinylbenzene copolymer (PDVB/VAc): the aqueous solution that adds 200mL1%PVA in the 500mL there-necked flask that reflux condensing tube, thermometer and mechanical stirrer are housed, be warming up to 45 ℃, under agitation add the mixing oil phase of 19g DVB, 1g polar monomer VAc, toluene (quality be monomer total mass 160%), normal heptane (quality be monomer total mass 40%) and azo isobutyronitrile (quality be monomer total mass 1.0%), regulate stirring velocity 140r/min, control the size of oil droplet.Slowly be warming up to 70 ℃ of polymerization 2h; Be warming up to again 87 ℃ of polyase 13 h; Continue to be warming up to 95 ℃ and boil ball 3h.Pour out product, use respectively hot water, cold water washing, and remove pore-creating agent with Petroleum ether extraction 24h, be drying to obtain precursor resin PDVB/VAc.Record the mean pore size 8.6nm of precursor resin, pore size distribution 1-50nm, Brunauer-Emmett-Teller(BET) specific surface area 572m
2/ g, pore volume 1.47cm
3/ g.
Vinyl acetate polar group is modified the preparation of crosslinked poly-divinylbenzene resin (PDVB/VAc_pc) after suspended double bond: take a certain amount of precursor resin, add enough 1,2-ethylene dichloride solvent-swollen to spend the night.At 40 ℃, add 0.2 times of anhydrous stannic chloride to make catalyzer, stirring and dissolving 1h.Be warming up to 85 ℃ of polymerization 12h.Replace washing resin 4 times with 1% hydrochloric acid soln and dehydrated alcohol respectively, with dehydrated alcohol extracting 10h, dry vinyl acetate polar group is modified crosslinked poly-divinylbenzene resin after suspended double bond.Record the mean pore size 6.5nm of PDVB/VAc_pc resin, pore size distribution 1-38nm, BET specific surface area 821m
2/ g, pore volume 1.84cm
3/ g.
The adsorption isothermal line of synthetic resins to rhodamine B: get one group of tool plug Erlenmeyer flask, add respectively therein the rhodamine B aqueous solution of 0.1000g dried resin and 50.00mL different concns, they are placed in to rotary water bath vibrator, and constant temperature oscillation 24h under 303K, makes absorption reach balance.Measure the absorbancy of the rear raffinate of absorption with ultraviolet-visual spectrometer at the maximum absorption wavelength 554nm place of rhodamine B, and be converted into the equilibrium concentration C of adsorbate according to typical curve
e, and calculated equilibrium adsorptive capacity q (mg/g)
e(mg/g).With equilibrium concentration C
efor X-coordinate, adsorptive capacity q
efor ordinate zou, make this resin under 303K to the aqueous solution in the adsorption isothermal line of rhodamine B.
Embodiment 5
The preparation of glycidyl methacrylate and divinylbenzene copolymer (PDVB/GMA): the aqueous solution that adds 200mL1%PVA in the 500mL there-necked flask that reflux condensing tube, thermometer and mechanical stirrer are housed, be warming up to 45 ℃, under agitation add the mixing oil phase of 18g DVB, 2g polar monomer GMA, toluene (quality be monomer total mass 200%), normal heptane (quality be monomer total mass 50%) and benzoyl peroxide (quality be monomer total mass 0.8%), regulate stirring velocity 115r/min, control the size of oil droplet.Slowly be warming up to 68 ℃ of polymerization 2h; Be warming up to again 85 ℃ of polymerization 4h; Continue to be warming up to 90 ℃ and boil ball 3h.Pour out product, use respectively hot water, cold water washing, and remove pore-creating agent with Petroleum ether extraction 24h, be drying to obtain precursor resin PDVB/GMA.Record the mean pore size 11.3nm of precursor resin, pore size distribution 1-80nm, Brunauer-Emmett-Teller(BET) specific surface area 521m
2/ g, pore volume 1.35cm
3/ g.
Glycidyl methacrylate polar group is modified the preparation of crosslinked poly-divinylbenzene resin (PDVB/GMA_pc) after suspended double bond: take a certain amount of precursor resin, add enough 1,2-ethylene dichloride solvent-swollen to spend the night.At 40 ℃, add 0.3 times of anhydrous stannic chloride to make catalyzer, stirring and dissolving 0.5h.Be warming up to 80 ℃ of polymerization 15h.Replace washing resin 3 times with 1% hydrochloric acid soln and dehydrated alcohol respectively, with dehydrated alcohol extracting 15h, dry glycidyl methacrylate polar group is modified crosslinked poly-divinylbenzene resin after suspended double bond.Record the mean pore size 12.8nm of PDVB/GMA_pc resin, pore size distribution 1-45nm, BET specific surface area 705m
2/ g, pore volume 1.67cm
3/ g.
The adsorption isothermal line of synthetic resins to rhodamine B: get one group of tool plug Erlenmeyer flask, add respectively therein the rhodamine B aqueous solution of 0.1000g dried resin and 50.00mL different concns, they are placed in to rotary water bath vibrator, and constant temperature oscillation 24h under 308K, makes absorption reach balance.Measure the absorbancy of the rear raffinate of absorption with ultraviolet-visual spectrometer at the maximum absorption wavelength 554nm place of rhodamine B, and be converted into the equilibrium concentration C of adsorbate according to typical curve
e, and calculated equilibrium adsorptive capacity q (mg/g)
e(mg/g).With equilibrium concentration C
efor X-coordinate, adsorptive capacity q
efor ordinate zou, make this resin under 308K to the aqueous solution in the adsorption isothermal line of rhodamine B.
Embodiment 6
The preparation of glycidyl methacrylate and divinylbenzene copolymer (PDVB/GMA): the aqueous solution that adds 200mL1%PVA in the 500mL there-necked flask that reflux condensing tube, thermometer and mechanical stirrer are housed, be warming up to 45 ℃, under agitation add the mixing oil phase of 16g DVB, 4g polar monomer GMA, toluene (quality be monomer total mass 120%), normal heptane (quality be monomer total mass 30%) and benzoyl peroxide (quality be monomer total mass 1.0%), regulate stirring velocity 120r/min, control the size of oil droplet.Slowly be warming up to 70 ℃ of polymerization 2h; Be warming up to again 85 ℃ of polyase 13 h; Continue to be warming up to 90 ℃ and boil ball 3h.Pour out product, use respectively hot water, cold water washing, and remove pore-creating agent with Petroleum ether extraction 24h, be drying to obtain precursor resin PDVB/GMA.Record the mean pore size 13.8nm of precursor resin, pore size distribution 1-100nm, Brunauer-Emmett-Teller(BET) specific surface area 504m
2/ g, pore volume 1.11cm
3/ g.
Glycidyl methacrylate polar group is modified the preparation of crosslinked poly-divinylbenzene resin (PDVB/GMA_pc) after suspended double bond: take a certain amount of precursor resin, add enough 1,2-ethylene dichloride solvent-swollen to spend the night.At 40 ℃, add 0.2 times of FERRIC CHLORIDE ANHYDROUS to make catalyzer, stirring and dissolving 0.5h.Be warming up to 85 ℃ of polymerization 12h.Replace washing resin 3 times with 1% hydrochloric acid soln and dehydrated alcohol respectively, with dehydrated alcohol extracting 14h, dry glycidyl methacrylate polar group is modified crosslinked poly-divinylbenzene resin after suspended double bond.Record the mean pore size 11.7nm of PDVB/GMA_pc resin, pore size distribution 1-41nm, BET specific surface area 621m
2/ g, pore volume 1.56cm
3/ g.
Synthetic resins is to Congo red adsorption isothermal line: get one group of tool plug Erlenmeyer flask, add respectively therein the Congo red aqueous solution of about 0.1000g dried resin and 50.00mL different concns, they are placed in to rotary water bath vibrator, and constant temperature oscillation 24h under 293K, makes absorption reach balance.Measure the absorbancy of the rear raffinate of absorption with ultraviolet-visual spectrometer at Congo red maximum absorption wavelength 496nm place, and be converted into the equilibrium concentration C of adsorbate according to typical curve
e, and calculated equilibrium adsorptive capacity q (mg/g)
e(mg/g).With equilibrium concentration C
efor X-coordinate, adsorptive capacity q
efor ordinate zou, make this resin under 293K to the aqueous solution in Congo red adsorption isothermal line.
Claims (10)
1. a polar group is cross-linked the preparation method who gathers divinylbenzene resin after modifying suspended double bond, it is characterized in that, the dispersion agent dispersed with stirring that first mixing oil of divinylbenzene monomer, polar monomer, toluene, normal heptane and initiator communicated in 40～50 ℃ of water after, under agitation condition, be first warmed up to 68～75 ℃ of polyreactions, be warmed up to again 83～87 ℃ of polyreactions, be more further warmed up to 90～95 ℃ and boil ball; After polyreaction completes, reaction product is washed, solvent extraction, obtains after polar group is modified suspended double bond being cross-linked poly-divinylbenzene resin precursor; Gained presoma, by after solvent-swollen, adds Lewis acid to carry out Friedel-Crafts reaction as catalyzer at 80～85 ℃; After Friedel-Crafts reaction completes, by products therefrom washing, solvent extraction, obtain after polar group is modified suspended double bond and be cross-linked poly-divinylbenzene resin; Described polar monomer is one or more in triallyl isocyanurate, glycidyl methacrylate, methyl acrylate, vinyl acetate; Described polar monomer is 5～20% of divinylbenzene monomer and polar monomer total mass.
2. preparation method as claimed in claim 1, is characterized in that, described polar monomer is 5～10% of divinylbenzene monomer and polar monomer total mass.
3. preparation method as claimed in claim 1, is characterized in that, described Lewis acid is iron trichloride, aluminum chloride, tin tetrachloride; Described Lewis acid add-on is 0.2～0.3 times of presoma quality.
4. preparation method as claimed in claim 1, is characterized in that, the total mass of first benzene and heptane is 150～250% of divinylbenzene monomer and polar monomer total mass, and the mass ratio of first benzene and heptane is 3～4:1.
5. preparation method as claimed in claim 1, is characterized in that, described initiator is benzoyl peroxide and/or azo isobutyronitrile, and the consumption of described initiator is 0.5～1.0% of divinylbenzene monomer and polar monomer total mass; Described dispersion agent is polyvinyl alcohol, and the mass percent concentration of described dispersion agent in the aqueous solution is 0.8～1.2%.
6. preparation method as claimed in claim 1, is characterized in that, at 68～75 ℃ of polyreaction 2～3h, at 83～87 ℃ of polyreaction 3～5h, boils ball 2～3h at 90～95 ℃; The Friedel-Crafts reaction time is 10～15h.
7. the preparation method as described in claim 1～6 any one, is characterized in that, after described polar group modification suspended double bond, crosslinked poly-divinylbenzene resin pore size distribution is 1～45nm, and mean pore size is 6～13nm, and specific surface area is 700～1200m
2/ g, pore volume is 1.6～2.5cm
3/ g.
8. the polar group that preparation method obtains as described in claim 1～6 any one is cross-linked an application that gathers divinylbenzene resin after modifying suspended double bond, it is characterized in that, described resin is applied to the organic adsorbate of polarity in the adsorbing and removing aqueous solution.
9. application as claimed in claim 8, is characterized in that, after described polar group modification suspended double bond, crosslinked poly-divinylbenzene resin pore size distribution is 1～45nm, and mean pore size is 6～13nm, and specific surface area is 700～1200m
2/ g, pore volume is 1.6～2.5cm
3/ g.
10. application as claimed in claim 8, is characterized in that, the organic adsorbate of described polarity is Congo red and/or rhodamine B.
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